Aluminum-chloride process



Oct. 25,

H. l. LEA ET AL ALUMINUM' CHLORIDE PROCESS (Jriginal4 Filed June 20. 1925 3 Sheets-Sheetl 502,0 J soa f 1 16467 Oct' '25 1927 H. l. LEA E1- AL 33 ALUMINUM CHLRIDE PROCESS original Filed June zo. 192s s sheeis-sheei2 Water f il [Ime/250m few/[gif Zea.

oct. 25,1927. YH. L LEA ET AL 33 ALUMINUM CHLORIDE PRXOCESS Original Filed June 20. 1925 5 Sheets-Sheet 3 Parenteel' oct. 25, 1927.

UNITED lSTATES PATENroFFlcE. 1

HENRY I. LEA, F SANTA. MONICA, CALIFORNIA, AND CLIFFORD W. HUMPHEEY, 0l RED BANK, NEW JERSEY.

ALUMINUM-cammini raocnss.

Appnoauon mea :une ao, 192s, serial No. 646,559. Renewed Marcil 1e, 1927.

This invention relates to processes for the production principally of alummum chloride. The present general object of the 1nvention concerned in this application and 5 in several co-pending and companion applications, hereinafter identified, is the eco-1 vl5 one for producing aluminum chloride, it is not to be understood that it may not be an object, or perhaps under other conditions the principal object, to produce one or more` of the other products of the process.

There are various procedures differing somewhat from each other by which Our process may be carried out; the process as a. whole will be best understood from the following detailed descriptions of preferred methods, rather than from any general statement that we may make in advance. However. for the purposev 0f generally distinguishing theprocesses of the several applications from each other we will make a general and preliminary statement 'of the distinguishing features of the several variations. It will be understood nevertheless that this statement is not intended in the least as a restriction or limitation upon the invention either as a whole or as to the specific aspects herein claimed, but is intended only to give a clear idea of the lines of delInarkation of the several specifi: deviations of the fundamental process and as between the specific claims of the several co-pending applications. This application is a oontinuation in part of our application on aluminum chloride process filed May 31st, 1922, Serial No. 564,762. Inthat application we have described alprocess including steps that may lbe said, in a broad way, to

amount to the-chlorination of a more or less J'dehydrated or more or less dehydrated and decomposed aluminum sulphate; and the specific variations in the methods have to do -With the various ways and means of effectving successive operations, as for instance, the

ways and means for obtaining the chlorine for the chlorination reaction, or the speclic kand that for purposes of identi ways and means of treating the original aluminum sulphate, 'as to whether it is decomposed or not before being chlorinated.

When we refer herein to aluminum sulphate it will be understood that we include that substance in whatever v,form it may be used. For instance, it may be in ores that carry the sulphate in such state that the ores themselves may be put directly into our process; or it may be in ores that require pre-treatment to separate certain other matters; or it may be in ores that may be put directly into the process and that may require one or 'two' additional steps during the process. Such for instance, is the ore alunite, an aluminum and potassium sulphate ore; and how such an ore may be treated is hereinafter set out. v

A typical form of the general process may, for` the purpose of this preliminary general statement, be described as follows the sulphur and oxygen may either come offas SO3 and SO2 and O. Then we chlorinate the oxide that we have obtained by decomposing `the sulphate, This'general aspect of the process is the subject matter of a copending companionapplication; also a continuation in part of said prior agplcation,

cation we here term application B, Serial No. 646,555, filed June 20, 1923. Just how and where the chlorine for chlorination is prferably obtained, durin the' steps of the process, is the particular su ject matter of an application, which, in this series, is identified as application C, Serial No. 646,556, filed June 20,1923; and this will be adverted to later. The chlorination' is carried out by subjecting the oxide, under suitable tempera ture, to the action of chlorine in the presence of carbon. The chlorine may be, and preferably is, in most variations of this process, free chlorine. chlorination step may be carried on without This also will be spoken of later.

But as we will set out the.

Whatever may be the immediate chlorinating agency, chlorination carried on in the presenceyof carbon is preferably carried on in the presence of hydrocarbons in the mann er and with vthe resulting advantages as hereinafter explained. The process, in itself, of chlorinating an aluminum oxideor an aluminum oxide carrying ore, in the presence of hydrocarbons, o r impregnated` with hydrocarbons, is made the specific subject matter of the claims of said prior application Serial No. r564,7 62, filed May 31, 1922, which for identification will be called in this speci- -lication, application A The chlorine for chlorination of the aluminum oxide produced by decomposition of the sulphate, is preferably obtained by using the i sulphur and oxygen product of that decomposition to makevhydrochloric acid;-and this may be done, as an illustration, through the step of making sulphuric acid. These procedures are capable of some'variations and are generally the characteristic subject matter of application C Serial No. 646,556,

-filed June 20, 1923.

Then, in the process where an SO compound or sulphuric acid is produced (as for instance, in the form of the process where the sulphate is decomposed as described in applications B and C) the S and O compound, either directly or through the step of forming sulphuric acid, may be used either wholly or in part, to react upon some vother aluminum compound, for instance, a'luminum silicate, to produce more aluminum sulphate for the process.4 This may be very economically done, particular] where the sulphur and oxygen compoun productionis more than is required forthe formation of the requisite amount ,of chlorinating agent. This variational featureof the process is the characteristic. subject vmatter of lcompanion application D? Serial No. 646.557, iled June20, 1923.

' .As another variation, thev sulphate may be chlorinated directly without decomposition'; and this vis subject matter of companion application E Serial No. 646,558,1i1ed June -20, 1923. And the sulphate ma Jfurther be treated for decomposition, and t e chlorinating'agent also formed in' what amounts to a single reaction, being in effect, a more or less complete summation of the several chlorinating agent forming reactions that are the characteristic subject matter of application o5 and a sulphate; and then the prodced oxide following.

may be chlorinated with the chlorinating agent. This 'last mentioned variation is the characteristic subject matter of the present application,identified in this series as application F.

All of the applications, herein identified as B to F inclusive, are divisional continuations in part or in whole of said application A, Serial No. 546,7 62. Since these divi-` sional applications relate more particularly to certainv variational forms of the process as hereinabovegenerally set out, we will in the specications endeavor onlyto set out the several subject matters necessary for the complete understanding of the respective claimed inventions and for an understanding .of the connection of the several divisional processes with each other. Accordingly, this present application has its descriptive matter directed more particularly to the process that involves characteristically the decomposition ofthe sulphate to produce an oxide and to the more or less simultaneous production of a chlorination agent with which the oxide is then chlorinated.

As will'be readily understood, our process may be carried on in any suitable apparatus; and so it is only for the purpose of clarifying the following detailed description thatwe illustrate a suitable apparatus in the accompanying drawin In these drawings there 1s a diagram w ich, for convenience of illustration is divided into several figures as. Fig. 1*, Fig. 1", Fig. 1, Fig. 1d; and Fig. 2 isa section showingl a form of chloride condensing chamber that may be used as herein explained.

In order to explain the Various forms in which this particular process may be carried out, andthe variations of which it is capable, We will first explain the general and typical form of processes which forms )more particularly the subject matters of applications B, and C of this series.

In the method that we shall describe first and' which maybe hereinafter referred toas method No. 1, we take aluminum sulphate,

and, placing it in a retort 10,heat it to a tempe-Iature sufficient to drive olf its water of crystallization; so that we have the reaction;

v A1,(S04)3+18(or lessHZO. l

We may say here that less than the maximum amount of water may be driven olf, because the sulphate does not always lcontain the maximum amount; and also because it may be that this reaction, like others in the process may sometimes not go through to absolute completion. This will be generally understood in'connection with all the The product hereiis a dehydrated aluminum sulphate that may be removed from time to time or preferably left in the retort for the next decomposition reaction. The retorts 10 may be arranged singly,'in pairs or more in a set so as to provide for more or less continuous operation. The water vapor that passes olf goes through pipe 9 into condenserpl?) or may go directly .to atmosphere.

Further application of 4heat to the dehydrated sulphate then-causesit to break up into aluminum oxide, sulphur dioxide and oxygen (or the aluminumoxide and sulphur trioxide, as hereinafter explained) as follows:

II: A1,(S04)3 +heat= A1203 SO2 30 (or=Al203 3S03) The temperature used for this reaction may Vary; we have found that a red heat is suitable, and a dull red heat or even lower may be suflicient (say about 600 C. or above). The temperature used depends on time element, the pressure (above or below atmosphere) maintainedl in the retort, and the extent of decomposition desired. We find that absolutely full decomposition :is not necessary or practically desired.

The sulphur dioxide and oxygen from this i operation pass through the pipe 11 to the cooler 12, which may be here an air or water cooler. The oxide may be removed from time to time to be put in the chlorinatingl retort; or chlorination, as hereafter explained, may be carried on in retorts 10.

Next the gases pass throughpipe 14 to a drying and cleaning tower 15- of any suitable kind, through which the gases rise upwardly and through which sulphuric` acid, ,or other drying medium, may be sprayeddown from the top; and the gases next are drawn out byan exhauster 16 and passed through a pipe 17 kintoa catalyzer 18. At the lsame time this exhauster draws in atmospheric air through a valve controlled pipe 19, the air passing through a washer 20, to cleanse and dry it. Catalyzer 18 is preferably of the type utilizing platinized asbestos. In this catalyzer the uncombined sulphur dioxide and voxygen are combined to form sulphur trioxide according to:

III: 3S02 +30+catalyzer= 3S0.

The oxygen theoretically required for this react1on may be fully supplied by the oxygen from the last preceding reaction; but we.

find that. an excess of oxygen (supplied here by the air) makes the reaction go on more necessary in starting to'warm the catalyzer, and then, when in operation, to somewhat cool it to maintain this temperature.

From the catalyzer 18 the sulphur trl# oxide passes through pipe 22 to another cooler 23 which may be either air or water cooled. We may state here that wherever a cooler is used in this` processl it may be desirable to use an air cooler as we thereby can more readily use the heat in the furnaces. From the cooler the sulphur/trioxide passes through pipe 24 into `an absorption tower 25. In the absorption tower the gases pass upwardly and sulphuric acid is sprayed downwardly; with the result that turning sulphuric acid is' formed, and this sulphuric acid collectingA in the bottom of the tower pasesout through pipe26into a' storage chamber 27 to which fwater may be controllably fed through 27a to change the fuming sulphuric into ordinary sulphuric of 66 B.

' gravity.`

These reactions are thus represented: (if they go to completion) IV 3S03 3H20 3H2S04.

If conditions in retortl 10 have been such as to produce S03 or to partially produce S03, then that S03 will, with sulphuric acid in 15, become 'H2S20T If S03 is produced entirely in l retort 10, then catalyzer 18 and cooler 23 and absorption tower 25 can be dispensed` instead of S02 and 0,

with; the I-I2S207 going directly from 15 Then rinto a retort or salt cake pan- 30 that is heated to about the saine temperature as the first retort we introduce an alkali chloride, for instance sodium chloride, and the sulphuric acid, in pro-per proportions for the following reaction which then takes place:

In this operation the chloride of sodium, potassium, calcium, magnesium 'or manganese may be used. If we use sodium chlor1de the result of thisoperation is to produce sodium sulphate and hydrochloric acid. The sodium sulphate is left in the retorts untll the charge is exhausted while the Vhydrochloric acid gas passes through pipe 31-into a drying chamber 32. V This drying chamber may be of bri 'k construction, illed with coke. The dried` hydrochloric acid vapor then passes through pipe 33 into a This heater may be heated with waste gases from theretorts. Then the dry heated H01 heater 34.

vM l floor 50"todropthrougli` outlet 62 into re# gas passes through pipel 35 to the second catalyzer 36 charged with broken brick, coke,"

pumice stone, or other suitable material Well soaked with a solution .of CuCl2 or other suitable catalyzing material. This catalyzer 36 is kept at a temperature of about 450 C., and also there is supplied to this catalyzer a suitable amount of air or oxygen so that the following takes place.;

VI.: (il-ICI -l- 30 -lcatalyzer= 3H20 -l- 6Cl.

The vapors and gases pass olii' through a pipe 37 which has a condensation bend 38 where the water is condensed and any remaining HC1 is thus taken 'o in solution and then the chlorine gas passes through pipe 39 into atower 40. This is a wooden tower lined with lead and filled with coke, and sprayed with water to cleanse the gases and ab'sorb any remaining HCl. Thence the gases pass through pipe 41 into a similar tower 42 which is sprayed with sulph'uric acid to dry the gases. Thence the gases are 'lead to a retort 43 which' is heated by any suitable means to a temperature of about red heat, say about 600 C. or more). And into this retort is also introduced carbon and the A1203 that has'been produced in retorts 10 when the dehydrated aluminum sulphate has ebeen broken up by heat. The carbon and A1203 are ground and thoroughly mixed to give intimate contact and briquetted if found ,desirable to prevent being carried over mechanically into the condensing chamber. The following reaction then takes place:

vii: A12o3+3c+6c1=A12c16+3co- The Aresult is the production of carbon monoxide gas and anhydrous aluminum chloride 1n vapor form. Thls aluminum chloride as fume passes into a lsublimating' y. chamber 44 where the aluminum chloride sublimes and the carbon monoxidepasses o from retort 43enter a chamber 56 thro through a pipe 45. This carbon monoxide may be used, for instance, asfuel inlany of the various furnaces.

It may be desirable to control the temperature of the aluminum chloride so as to control its linal physical form; and in Fig. 2.

we have shown vone form of a paratus suitable for that purpose. The c loride vapors h pipe 55. This chamber has a brick top 51 heated by a heating jacket 52 receiving waste gases from combustion under the retort, and

l Whose temperature may be controlled by any suitable damper arrangement, for instance. The conical bottom of chamber 56 is steam jacketedat 57, steam (or other vapor) being admitted at 58 and exhausted through a trap at 59. By controlling the .pressure any selected temperature may be maintained at 1 the conical floor of chamber 56. A revoluble scraper 60 serves to scrape the chloride off chloride, which is about- 183 ceiver63. The residual gases (CO pass l out through 14. vCool' inert gases or 1nstance, CO or N) may be introduced at 65. The various operations follow:

(a) Pass cool gas through 52, air cool the jacket 57 and introduce cool gas at 65, and then all or practically `all the chloride will be sublimated in finely divided form.

(b) Heat top ofchamber so that inside temperature Lis above the boiling oint of the Cr.) Floor ,50

A is maintained slightly below the ymelting point (178 0.); andthen the major portion of the chloride will be thrown down as a cr stal. y l A T e device above described also forms one means for obtaining fractional condensation separation of certain final products of certain methods herein described. Fo-r in-l stance, where aluminum chloride and certain may be at least partially separated by maintaining the proper temperature in the chamber,its roof and floor; or, of course, they may the chlorination of the oxide obtained by,

dehydratin'g and decomposing aluminum sulphate. In the particular procedure de-x scribed we obtain thechlorine for the chlorination from hydrochloric acid which in turn is formed from sulphurio acid and sodium chloride, and the sulphuric acid'is ,J formed from the sulphur'dioxide and oxygen sulphur compounds are final products, .theyI aluminum chloride A (Equationv (and/or S03) that are driven oli when the aluminum sulphate is reduced to aluminum' oxide; and these particular things, with their' l variations, form more particularly the subject matter of application C, herein above identified. However, as such variations may form a part of the process as practically carried out, we mention typical ones.

Generally speaking, we nd that` as ourprocess involves the chlorination of aluminum oxide obtained by decomposition of dehydrated aluminum sulphate, we can carry on the operations at much lower temperature than any other process 'of which we are aware; and we find also that such decomposed sulphate lends itself very readily to easy chlorination. It will be Iunderstood that in all forms of'our process, anhydrous aluminum sulphate may be the starting point of onr'actual operations; the sulphate may be dehydrated previously.

We may say here' that in the operation of Methods in which the sulphate is decomposed simultaneous@ with the production of the chlorimtiug agent. One of the methods that form more articularly the specific subject matter of 's 4application involves the same first step as before described, that is, the'dehydration of the aluminum. sulphate by heat., Thelsecond step in this vmethod however, involves putting the undecomposed aluminum sulphate directly into reaction with a chloride, and.,

" treated in the retort in admixture with a this may be done either with or without the presence of Water.. If water 1s used one of the results of this step is to 'produce hydrochloric acid. If water is not used chlorineL thus if we use sodium chloride, and if water is used,'theA reaction is as follows:

It will be unnecessary to give reaction equations using other chlorides as they will be readily understood.

This reaction step may be carried outin a retort such as those previously descrlbed,

'heated to about the temperature hereinbe- 4 fore stated, that is, to a temperature of about 600 C. or more.

ing reaction then we may have typical reaction;

The aluminum oxide and the sodium or other sulphate are separated by lixiviation and the oxide then re-drled,

lpreparatory to "being chlorinated.

In this form of-the process, producing hydrochloric acid, the last two steps may be the same as hereinbefore stated; that is,\a reaction to produce chlorine from the hydrochloricv acid,A and-then the chlorinating re action using the chlorine to chlorinate the.

produced oxide.

If water 1s not used inthe oxide reduc-A the fo owing In .this casethe reaction is not always complete and the .chlorine and sulphur .The aluminum oxideA is leached-out of the be used to producemore hydrochloric acid orv chlorine may be obtained furnace, with sulphuric acid or chloride may bel manufactured or either the acid or chlorine may be obtained from other sources.

In any of these processesa natural occurring ore may be substituted for the-alumi-l i num sulphate, after treatment to free it, of

other ingredients and to reduce it to alumi-l num sulphate orv substantially to aluminum sulphate. Or, for instance, certain sulphate ores may be put through a more or less special process similar to .those above exl plained. `For. instance, alunite may be used.

This ore may be described, as. a sulphate of aluminum and potassium, and it may be presence of water (steam) -to form aluminum oxide, potassium sulphate and hydrochloric acid. The potassium sulphate may be'spa-y rated from the oxide by lixiviation and the oxidethen dried to go into the chlorinat'in reaction. By regulating the amount o H2O, .the hydrochloric acid can be taken off largely in gaseous state, so that on drying it may be taken directly, as before explained, l

to the hydrochloric acid catalyzer and there, in reaction with air'or oxygen, caused'to form chlorine and water.

Or, by omitting the water in the foregoing reaction, and b first having thoroughly dried both the a unite ore and the chloride, then fre chlorine results, in a -certain amount, ti'om this reaction instead ,of hydrochloric acid. Sulphur dioxide also results from this last operation and it may be sepa.

rated out by absorption 4or liquefaction and then the sulphur dioxide may -b'e used for makin more chlorine as before explained.

We lhave explained inthe said prior ap plication how some or all of the sulphur yno oxygen content of the sulphate or ores, when driven olii' in the ,decomposin reaction, may phate for the process. Thisparticular'aspect of ourprocess, including also the production directly of more yaluminum oxide for the process is the'peculiar sub'ect matter o'f identified ap- "plication D; utvthere v"is one feature of vthat process that is similaryto the specificl process and methods herein set out, and that forms specific lsubject matter of' this present application.'4 In using". the vsulphur oxygen contentto produce more aluminum oxide for mass of sodium sulphite and the oxide thenwthe process` there is a reaction wherein an dried and then chlorinated in accordance with the.,chlorination step as before -def scribed. Any deficiency of chlorine may be supplied from' van Youtside source. Where aluminum sulphate is .decomposed to produce aluminum oxidesimultaneously with the production of the chlorinating agent. Generally speaking, "1n said`y application D an sulphate'pre is used we ,have explained how the sulphur oxygen4 content may be used to react on any aluminum silicate or aluminum bearing ore suitable for making aluminum sulphate, to produce aluminum sulphate but thisv'will not need particular descriptlon here. But, in usin the sililtphuroxy en content, e ither who y or pa y, to pr ucc more aluminum compound for chlorination, wemay o one step further,- and instead of pro ucing aluminum sulphate, we may directly produce the' aluminum oxide and @simultaneously peroduce the chlorinating agent. This may done at a single operation, using some pr all of the sulphur oxygen content, as folowsz or, 3SO2+3O may be used )in place of 3SO3 with the same results as above. Or, if thegen content is irst put into sul- (as has been hereinbefore exgeneral process) then the opsulphur o phuric aci plained in the eration is course be used as will'be readily understood.

These operations ma becarried out in the retorts at substantial the same temperatires as before specified. The aluminum 'ox- 1 e the sulting product;- and then of course the aluminum oxide is 'dried 'before being put through the chlorination step.

. It will be seen that' in this particular variation of the process, just as in those before given, we have an operation in which anl aluminum ore is broken down to `aluminum oxide and thechlorinating agent is produced in the same operation.

It will' be understood that, although we have here now stated various forms of procroduced is separated by leaching from ess, that we have-given these various forms by way of illustration only; and that the `all of the possible methods that' might be thus worked out. .v I

Having described a preferred form of'or inventions, we claim:

1. A process that includes trea'ti g deh drated aluminum sulphate with a chloride under heat to form aluminum oxideand a chlorinating agent, and then chlorinatin'g the aluminum oxide with said chlorinating agent. A 2. A process that includes treating dehydrated aluminum sulphate with a chloride' and water under heat to form aluminum oxide and hydrochloric acid, then chlorinating the oxide with chlorine obtained from the hydrochloric. acid.

. 3. A process that includes partially dehydrating aluminum sulphate, then causlng it to react with a chloride to form aluminum oxide, HC1 and a sulphate,.separating the oxide and sulphate and chlorinating the oxide with chlorine made from the HC1.

4. A process -that includes dehydratingkd aluminum sulphate, vforming hydrochloric acid and aluminum oxide by reactions between the dehydrated aluminum sulphate and water and a chloride; and chlorlnating the aluminum J'oxide with -chlorine producedY from thevhydrochloric` acid, to form anhydrous aluminum chloride. f

In witness that we claim the foregoing we have hereunto subscribed. our names this 7th day of June, 1923.

HENRY I. LEA.

' CLIFFGRD W. 

